Arylide of hydroxy aromatic acids and method of making same



Patented Dec. 12,1933 1 i 1,938,901.

AR'YLIDE' or HYDROXY AROMATIC horns AND METHOD OF MAKING SAME Ernest F. Grether, Midland, Mich, assignor to The Dow Chemical Company, Midland, Mich., I a corporation of Michigan No Drawing. Application November 22, 1930 Serial No. 497,604

8 Claims. (01. 260-'124) The present invention is concerned with new i Example 1 dye intermediates from which can be prepared H 7 azo s f ir t-dev lop d ype by pl The 2.3-hydroxynaphthoic' acid arylide of 3.4- V diazo components thereinto, particularly with hydichloroanmne is prepared by condensing said droxy aromatic carboxylic acid arylides and acid and amine in equimolecular proportions with 60' 9 panicularlf W z-3hydroxynaphthoic the aid of phosphorus trichloride in the presacld 53-4d1ch1oroan1hde- .ence of toluene at the refluxing temperature Wen known that azo dyes whlch are fflst thereof in the usual manner, whereby the desired to hght and washmg may be produced by couphng arylide forms as a solid phase intermixed with 13- diazo components, i. e. diazotized aromatic a liquid mediurm The melting point f the n- 5 amines, into arylides such as Naphthol AS, the fled arynde-wasifound to be 0 latter being the anmde of S P Cotton yarn is impregnated with a slightly alw In a co'pendmg apphcatlon- Selim} kaline solution of the above arylide to which may 404,874, filed November 41 1929, I h dlsclosed be added advantageously, but not necessarily,

15 that 3.4-dichloroan1line and its substituted deformaldehyde and/01; other fixative, g Turkey 70 rivatives may be employed in the Preparation of red oil or an aluminum salt. Said yarn is then the abovesaid arylides, and have claimed therein d' m a d solution r e from the new and useful dyes formed by coupling methyl-i-chloroaniline. The dye develops on azotized or 'polyazotized aromatic amino comthe fiber and has a scarlet color, th'e'formul'a pounds with such arylides. I am now claiming being, 751

herein such arylides derived from 3.4-dichloroanilines and hydroxy aromatic acids by condensation or other suitable manner, the probable gen- H, eral formula of such intermediates being represented as, I r -i=N C OH C1 3 on oi V \GONHOC CONE Cl Example 2 35 wherein the formula represents a product pre- -In a manner similar to described in Exam- V pared by condensing 3,4- 11 1 1 1 t a ple 1, dianisidine is tetrazotized and coupled into hydroxy aromatic acid My invention, then, the same arylide, the dye which develops on the consists of the steps and products hereinafter fiber, being m e ue in e f mu a 40 fully described and particularly pointed out in for the dye the claims, the following description setting forth but several of the various ways in which the principle of my invention may be used.

The herein described new arylides may be pre- 4 pared from the aforementioned 3.4-dichloroani- I lines and hydroxy aromatic acids, e. g, 2.3-hy- 0H 01 droxynaphthoic acid, in any of the ordinary ways, G for instance by condensing the amine and acid CONE" C1 by means of phosphorus trichloride in thepres- 011 50 ence of an aromatic hydrocarbon, e. g. toluene, 2

as a solvent and/ or diluent, or by condensing such amine with 2.3-hydroxynaphthoyl chloride. Example 3 A preferred manner in which my invention may be carried out is illustrated in the following 7 Similarly, as described in Example 1, 2-nitro-4- 55 specific examples. ethoxyaniline is diazotized and coupled into the The Standard Color Card of America (1928 Ed.) issued by The Textile Color Card Association of the United States, Inc. is used to designate the colors of the above dyes.

In like fashion, I have prepared other dyes of the same general type from the abovementioned arylides, by coupling thereinto other diazo components, e. g. 2-chloro-4-nitraniline, 3.4-dichloro- 6-nitraniline, and aminonaphthyl-phenyl ether.

The herein described dyes prepared from my new intermediate compounds dye fibers in clear, bright, and fast shades, the color depending on the particular diazo component employed. While cotton fibers have been referred to in the example as the material to be impregnated with an alkaline solution of the herein described new arylides, other natural .or synthetic fibers may likewise be treated therewith, such as silk, wool, rayon, and the like. I

Furthermore, I do not limit my invention to the specifically aforementioned intermediates. Any diazo component, suitablefor use in preparing azo dyes, may be employed for combining with the herein described coupling components or arylides derived from other similar amines, i. e. the bromo derivatives analogous to the specifically mentioned chloro compounds. Moreover, the several groups and residues of such arylides may be further substituted as by alkyl or halogen groups.

Other hydroxy aromatic acids, such as salicyclic acid, or substitution products thereof, e. g. halogen, nitro, and/or alkyl derivatives, likewise may be employed as arylide components.

In brief, my invention broadly involves arylides of the type, 1

OH X wherein R represents the residue of an aromatic hydrocarbon, X represents a bromo or chloro group, and wherein the several groups and residues may be further substituted.

Other modes of applying the principle of my invention may be employed instead of the one explained, change being made as regards the details employed, provided the steps or ingredients stated by any of the following claims or the equivalent of such be employed.

I therefore particularly point out and distinctly claim as my invention:-

1. The method of making an arylide, which comprises condensing a 3.4-diha1oaniline with a hydroxy aromatic acid.

2. The method of making an arylide, which comprises condensing 3.4-dichloroaniline with a hydroxynaphthalene carboxylic acid.

3. The method of making an arylide, which comprises condensing 3.4-dichloroaniline with a hydroxynaphthalene carboxylic acid in the presence of phosphorus trichloride and a hydrocarbon diluent.

4. The method of making an arylide, which comprises condensing 'BA-dichloroaniline with 2.3-hydroxynaphthoic acid.

5. The method of making an arylide, which comprises condensing 3.4-dichloroaniline with 2.3-hydroxynaphthoic acid in the presence of phosphorus trichloride and toluene.

6. As a new product, an arylide of the general formula,

I 7 01 on CONE-@431 8. As a new product, 2.3-hydroxynaphthoylamino-3.4-dichlorobenzene, having the formula,

OONH -Cl ERNEST F. GRETHER.

Certificate of Correction Patent No. 1,938,901.

ERNEST F. GRETHER It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Page 1, lines 26 to 34, strike out the formula and insert instead same page, lines 76 to 86, strike out the formula and insert instead and that the said Letters Patent should be read With these corrections the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 13th day of February, A. D. 1934.

(SEAL) therein that F. M. HOPKINS, Acting Commissioner of Patents.

December 12, 1933. 

